N-alkylether 2-pyrrolidones

ABSTRACT

The present invention deals with the composition, application and process for preparation of novel ether containing lactam compounds, useful as surface active agent. Compounds of this invention have emulsification, wetting, softening, anti-tangle, conditioning, ability to complex and solubilization properties. In some of the compounds of the present invention there is ethylene and propylene oxide in the molecule backbone resulting in an inverse cloud point. This property allows the formulator to get minimum solubility and maximum substantivity at higher use temperatures, and more solubility and lesser substantivity at lower temperature.

This application is a continuation in part application of applicationSer. No. 07/551,026 filed July 11, 1990, now U.S. Pat. No. 4,983,384,which is a continuation in part of Ser. No. 07/333/539 filed Apr. 5,1989, now U.S. Pat. No. 4,958,032 issued Sep. 18, 1990.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention deals with the composition, application andprocess for preparation of novel ether containing lactam compounds,useful as surface active agents. Compounds of this invention haveemulsification, wetting, softening, anti-tangle, conditioning, abilityto complex and solubilization properties. In some of the compounds ofthe present invention there is ethylene and propylene oxide in themolecule backbone resulting in an inverse cloud point. This propertyallows the formulator to get minimum solubility and maximumsubstantivity at higher use temperatures, and more solubility and lessersubstantivity at lower temperature.

2. Description of the Art Practices

THe reaction of aliphatic primary amines with butyrolactone is wellknown to those skilled in the art and is disclosed in variouspublications and a series of patents by Rajadhyaksha, including U.S.Pat. No. 4,423,040 issued Dec. 27, 1983, which teaches that1-substituted azacyclohexan-2- ones can be prepared and used asphysiologically active agents. Related patents to Rajadhyaksha includeU.S. Pat. Nos. 4,525,199; 4,461,638; 4,444,762; 4,562,075; 4,316,893;4,122,170; 4,405,616; and 4,415,563. Since there are no ether noralkoxylate groups in the disclosed compounds, none of the referencedpatents teach the compounds of the present invention.

Lower alkyl pyrrolidones have found applications as low toxicity aproticsolvents. However the absence of a hydrophobe on the molecule make thelower alkyl products non-surface active.

3. Object of the Invention

One aspect of this invention relates to a particular group on ethercontaining N substituted lactams and alkoxylated versions of thesematerials. An additional aspect of the invention is the application ofthese materials as surface active agents in specific fields were thealkoxylated ether linkages give superior functional attributes. Oneadditional aspect of the invention relates to the incorporation of aregiospecific beta branched ether amine based upon guerbet alcohols intothe ether lactam. As will become apparent, the liquidity and highmolecular weight of the guerbet moiety, makes these products well suitedfor applications like personal care were low irritation andsubstantivity is important.

Another aspect of the invention is to provide products which have aninverse cloud point in aqueous solution. The inverse cloud pointphenomena which occurs as one heats an aqueous solution to a criticaltemperature has been well documented. More detailed descriptions of thisare found in standard textbooks, such as A.M. Schwartz and J.W. Perry"Surface Active AGents", Vol. I (1949); and "Surface Active Agents andDetergents" Vol. II (1958). Interscience Publishers, New York, thedescriptions of which are incorporated herein by reference.

The presence of ethylene and propylene oxide in the molecule backboneresults in an inverse cloud point. This property allows the formulatorto get minimum solubility and maximum substantivity at higher usetemperatures, and more solubility and lesser substantivity at lowertemperature.

4. The Invention

The compounds of the current invention conform to the followingstructure; ##STR1##

The cyclic nature of these compounds, the presence of the ether linkage,the degree of alkoxylation if any, mole ratio of ethylene oxide topropylene oxide, the exact location of the ether linkage, and thehydrophobic nature of the "R" group taken together result in maximumefficiency and flexibility of properties as surface active agents. Thecritical micelle concentration, i.e. the concentration at which micellesbegin to form are very low for these materials (approx. concentration of5×10-5). The synthetic route used for the preparation of the compoundsof the present invention requires that three and only three methylenelinkages are between the nitrogen in the lactam ring and the etherlinkage. As will become clear later, this is a consequence of how theether amine is prepared. The ether amine is prepared by the reaction ofacrylonitrile reaction with an alcohol or alkoxylated alcohol followedby hydrogenation to the amine reactant used in the process of thepresent invention.

THe resonance forms which result from this exact structure results inunique properties. The resonance forms of the lactam (carbonyl group andnitrogen group making a cyclic amide) and the electronegative etherlinkage in the specified location, taken together result in a highdipole moment and enhanced complexation capabilities. The added hydrogenbonding of the ethylene oxide and propylene oxide groups also increasesthe complexation ability and renders upon the molecule the property ofan inverse cloud point, the significance of which will become apparent.

The compounds of this invention can be tailored to specific applicationsby the selecting the proper "R" group, the degree of alkoxylation ifany, as well as the relative amounts of ethylene oxide and propyleneoxide present in the molecule. These factors comes from the aminecompound chosen to be reacted with butyrolactone.

The compounds of the present invention condition fiber by virtue of thesubstantivity of the compound to the fiber. The conditioning propertieswhich are desirable include softening and antistatic properties. Thefibers include hair, cellulosics, polyesters and acrylics.

The concentration of the compounds of the invention will ranges from 0.1to 50%, and in a preferred range from 1.0 to 25.0%.

The preparation of the other amines and alkoxylated ether amines areknown to those skilled in the art and are items of commerce marketed byTomah Products. The technology is summarized by the following equation;##STR2##

One specific group of ether amines, commercially available from TomahProducts, useful in the preparation of the compounds of this inventionare Guerbet Alcohols and their alkoxylates. These regiospecifically betabranched alcohols have been known since the 1890's when Marcel Guerbetfirst synthesized them. (M. Guerbet, C.R. Acad. Sci. Paris, 128, 511;1002 (1899)). These materials are high in molecular weight and areliquid to very low temperatures. The guerbet reaction gives veryspecific branching in the alcohol as shown; ##STR3##

As can be seen by the above reaction the molecules have substitution onthe second carbon from the hydroxyl group. This branching has been foundto be critical to the preparation of a product having the desiredproperties. If the branching were on the same carbon as the hydroxylgroup, the hydroxyl group would be a secondary one and would be veryhindered and has low reactivity. As one moves the branch position awayfrom the beta carbon, the liquidity, and substantivity to hair and fiberdecreases.

Guerbet alcohols that are the reaction product of one specific rawmaterial alcohol will result in a so called "homo-guerbet". In this caseR' and R" are identical. If the starting alcohols used in the guerbetreaction are of differing molecular weights a so called "hetero-guerbet"results. This type of guerbet has a mixed distribution of all possiblecombinations of alcohols. For this reason R and R' in the genericformula may be the same or different. ##STR4##

The use of guerbet derived either amines to prepare compounds of thisinvention results in substantive liquid products. The high molecularweight of the hydrophobe allows for better oil solubilization usingthese surfactants over conventional nonionic surfactants.

5. Examples

    ______________________________________                                        Raw Material Examples                                                         Reactant A                                                                     ##STR5##                                                                     Example     R        x          y   z                                         ______________________________________                                        A           C.sub.10 H.sub.21                                                                      0          0   0                                         B           C.sub.18 H.sub.38                                                                      2          2   2                                         C           C.sub.20 H.sub.42                                                                      0          0   0                                         D           C.sub.16 H.sub.34                                                                      0          6   0                                         E           C.sub.18 H.sub.36                                                                      0          6   4                                         F           C.sub.10 H.sub.21                                                                      3          6   3                                         G           C.sub.18 H.sub.34                                                                      0          3   0                                         H           C.sub.18 H.sub.34                                                                      6          0   0                                         I           C.sub.18 H.sub.34                                                                      1          1   1                                         ______________________________________                                        Guerbet Alcohol Ether Amines                                                   ##STR6##                                                                     Example  R'        R"     x       y    z                                      ______________________________________                                        J        C.sub.8   C.sub.10                                                                             0       0    0                                      K        C.sub.8   C.sub.10                                                                             1       1    1                                      L        C.sub.8   C.sub.10                                                                             0       5    2                                      M        C.sub.8   C.sub.10                                                                             5       5    5                                      N        C.sub.8   C.sub.10                                                                             10      10   10                                     O        C.sub.11  C.sub.13                                                                             0       0    0                                      P        C.sub.11  C.sub.13                                                                             1       1    1                                      Q        C.sub.11  C.sub.13                                                                             0       5    2                                      R        C.sub.11  C.sub.13                                                                             5       5    5                                      S        C.sub.11  C.sub.13                                                                             10      10   10                                     T        C.sub.16  C.sub.18                                                                             0       0    0                                      U        C.sub.16  C.sub.18                                                                             1       1    1                                      V        C.sub.16  C.sub.18                                                                             0       5    2                                      W        C.sub.16  C.sub.18                                                                             5       5    5                                      X        C.sub.16  C.sub.18                                                                             10      10   10                                     ______________________________________                                    

There are two alternative processes useful in the preparation of thecompounds of the present invention. One is conducted under pressure,leaving the reaction products in a sealed reaction vessels, the other isrun at atomospheric pressure. The latter is generally conducted using asplitter and recycle loop wherein utyrolactone is separated fromreaction product eater and is returned to the reaction vessel. The wateris collected in a receiving flask. The following are suggested processembodiments of present invention.

General Reaction Procedure #1 (Autoclave)

Into a stainless autoclave was introduced the specified amount of thespecified ether amine. and 95.0 grams of butyrolactone. The autoclavewas sealed and 100 psig nitrogen was applied. The contents were heatedto 275C. and held for eight hours, during which time the pressure roseto about 480 psig. The reaction product was distilled to give a productwhich conformed to the following generic structure;

    ______________________________________                                         ##STR7##                                                                     Example Number   Reactant A Ether amine                                       ______________________________________                                        1                539.0 Grams Example A                                        2                622.0 Grams Example B                                        3                602.0 Grams Example C                                        4                654.0 Grams Example D                                        5                856.0 Grams Example E                                        6                833.0 Grams Example F                                        7                505.0 Grams Example G                                        8                592.0 Grams Example H                                        9                435.0 Grams Example I                                        10               383.0 Grams Example J                                        11               486.0 Grams Example K                                        12               766.0 Grams Example L                                        13               1118.0 Grams Example M                                       14               1413.0 Grams Example N                                       15               485.0 Grams Example O                                        16               632.0 Grams Example P                                        17               868.0 Grams Example Q                                        18               1220.0 Grams Example R                                       19               1955.0 Grams Example S                                       20               624.0 Grams Example T                                        21               771.0 Grams Example U                                        22               1007.0 Grams Example V                                       23               1799.0 Grams Example W                                       ______________________________________                                    

General Reaction Procedure #2 (Atmospheric)

Introduce into a glass flask the specified number of grams of Reactant Aand 150.0 grams of butyrolactone. The contents of the flask are thenheated to 75C. and held for eight hours. Subsequently, the temperaturewas raised to 250C. slowly over 4 hours. Then vacuum was applied and thereaction product was distilled to give a product which conformed to thefollowing generic structure;

    ______________________________________                                         ##STR8##                                                                     Example Number   Reactant A Ether amine                                       ______________________________________                                        24               539.0 Grams Example A                                        25               622.0 Grams Example B                                        26               602.0 Grams Example C                                        27               654.0 Grams Example D                                        28               856.0 Grams Example E                                        29               833.0 Grams Example F                                        30               505.0 Grams Example G                                        31               592.0 Grams Example H                                        32               435.0 Grams Example I                                        33               383.0 Grams Example J                                        34               486.0 Grams Example K                                        35               766.0 Grams Example L                                        36               1118.0 Grams Example M                                       37               1413.0 Grams Example N                                       38               485.0 Grams Example O                                        39               632.0 Grams Example P                                        40               868.0 Grams Example Q                                        41               1220.0 Grams Example R                                       42               1955.0 Grams Example S                                       43               624.0 Grams Example T                                        44               771.0 Grams Example U                                        45               1007.0 Grams Example V                                       46               1799.0 Grams Example W                                       47               2094.0 Grams Example X                                       ______________________________________                                    

Application

Wet Comb Out Test

A laboratory test is conducted to screen the wet comb properties of arepresentative member of the family of novel compounds. Hair swatchesare purchased from a supply of human hair from the same head. Each testswatch contains 7 grams of hair and is 11 inches in length. The hair istied tightly 1 inch from one end with string. The swatch is pre-cleanedwith a 3% solution of ammonium lauryl sulfate. Subsequently, the swatchis washed under running tap water. The hair is then squeezed out andwhile still damp dipped into a 200 ml solution of 0.2% activequaternary. Another rinse is made, then the swatch is blotted dry. Theswatch is then treated by holding the hair swatch, combing the hair asrapidly as possible while alternating the side of the swatch combed. Thetime needed to get one smooth free stroke without tangling is recorded.Typical results for the standard quaternary compounds used in hairconditioning (stearyldimethylbenzyl ammonium chloride) range from 12-14seconds.

    ______________________________________                                        Rinse Conditioner (Wet Comb Out Test)                                         Product          Time in Seconds                                              ______________________________________                                        Product Example #17                                                                            12                                                           Product Example #33                                                                            14                                                           Stearyldimethylbenzyl                                                                          12                                                           ammonium chloride                                                             ______________________________________                                    

As can be seen, the compounds of invention give significant conditioningproperties to hair, and coupled with their mild nature with regard toskin and eyes, makes it a prime candidate for cosmetic applications.

What is claimed is:
 1. A substituted lactam conforming to the followingformula; ##STR9## wherein; R is a alkyl having from 10 to 36 carbonatoms.
 2. A compound of claim 1 wherein R has 12 to 30 carbon atoms. 3.A compound of claim 1 wherein R has from 12 to 26 carbon atoms.
 4. Acompound of claim 1 wherein R is ##STR10##
 5. A compound of claim 1wherein R is ##STR11## wherein a and b are integers from 6 to
 17. 6. Acompound of claim 1 wherein R is CH₃ --(CH₂)₁₁ --.
 7. A compound ofclaim 1 wherein R is CH₃ --(CH₂)₁₁ --.
 8. A compound of claim 1 whereinR is CH₃ --(CH₂)₁₃ --.
 9. A compound of claim 1 wherein R is CH₃--(CH₂)₁₅ --.
 10. A compound of claim 1 wherein R is CH₃ --(CH₂)₁₇ --.11. A compound of claim 1 wherein R is CH₃ --(CH₂)₁₉ --.